CN106133196B - The steel wire rod and its manufacturing method of epithelium with excellent corrosion resistance and processability - Google Patents

The steel wire rod and its manufacturing method of epithelium with excellent corrosion resistance and processability Download PDF

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Publication number
CN106133196B
CN106133196B CN201580015991.3A CN201580015991A CN106133196B CN 106133196 B CN106133196 B CN 106133196B CN 201580015991 A CN201580015991 A CN 201580015991A CN 106133196 B CN106133196 B CN 106133196B
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China
Prior art keywords
epithelium
steel wire
wire rod
water
tungsten
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CN201580015991.3A
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Chinese (zh)
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CN106133196A (en
Inventor
伊藤弘高
柳泽佳寿美
小泽敬祐
椎桥庆太
小见山忍
畠山豪
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Kobe Steel Ltd
Nihon Parkerizing Co Ltd
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Kobe Steel Ltd
Nihon Parkerizing Co Ltd
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Abstract

Present invention offer can take into account stringiness, pin, steel ball and the corrosion proof steel wire rods and its manufacturing method with lubricating film such as processabilities and long-term rust prevention such as draftability are thinned.A kind of steel wire rod, it is characterized in that, it is the steel wire rod with not phosphorous epithelium, and above-mentioned epithelium successively includes from steel wire rod side: be made of the oxide of zirconium and/or hydroxide and film thickness be lower layer's epithelium of 1~200nm and containing silicon and tungsten and tungsten/silicon mass ratio 1.3~18 range upper layer epithelium；And a kind of manufacturing method of steel wire rod, which is characterized in that it is the manufacturing method of above-mentioned steel wire rod, and the surface of steel wire rod is made to contact range of the pH 2.5~5.0 and the water system chemical synthesis treatment liquid dissolved with water-soluble zirconium compound and form lower layer's epithelium.

Description

The steel wire rod and its manufacturing method of epithelium with excellent corrosion resistance and processability
Technical field
The present invention relates to steel wire rods and its manufacturing method that surface has not phosphorous epithelium.
Background technique
In the plastic processing of steel wire and steel wire rod, metal surface is tempestuously mutual each other (especially mold and processed material) The friction generated when friction becomes the reason of power consumption of polymer processing increase, heat release, ablation phenomen etc., therefore is using to reduce frictional force The various lubricants of target.For lubricant, all the time using oil, soaps etc., is formed and flowed and being supplied to rubbing surface Body lubricating film gradually decreases frictional force, but due to expanded surface area and with highly exothermic, just in the modeling of high surface pressure lower slider Property processing for, be easy that ablation phenomen occurs since lubricity is insufficient, lubricating film disconnects etc..Therefore, preparatory with solid epithelium The technology on metal material for coating surface has routinized, and the solid epithelium is that have sufficient epithelium intensity, even if high surface pressure Under also between mold and the interface of processed material to be not susceptible to lubricating film disconnection, can be avoided that metal is mutual directly to be connect Inorganic epitheliums such as the borate epithelium of touching, phosphate crystal epithelium etc..It especially include the Composite Skin of zinc phosphate coat and soap layer Film (hereinafter sometimes referred to chemical conversion treatment epithelium) has high working property and corrosion resistance, is widely used.
On the other hand, in recent years, the further decreasing of power consumption of polymer processing and strong degree of finish, the reply of difficult processing material, skin The feature of environmental protection of membrane process is (for example, phosphate treated is deposited in environmental protection due to generating the industrial wastes such as a large amount of slurry In problem), the phosphatizing of bolt etc. (after high-intensitive bolt head processing when the phosphorus residual of epithelium ingredient, the phosphorus in heat treatment Into in steel, become the cause of brittle break) countermeasure etc., the requirement to solid epithelium is varied, higher and higher, for these It is required that developing the solid epithelium with high lubrication while considering environmental protection.The technology is only by processed material Surface coating water system plastic processing lubricant, drying easy process and form the epithelium with high lubrication.
Patent document 1 discloses the formation of a kind of metal material plastic processing water system lubricating film inorganic agent and the epithelium Method, which is characterized in that it is the composition for dissolving or being dispersed with (A) water-soluble inorganic salt He (B) wax in water, solid weight Amount is than (B)/(A) in the range of 0.3~1.5.
In addition, patent document 2 discloses a kind of metal material plastic processing water system lubricating film inorganic agent and the epithelium Forming method, which is characterized in that containing alkali borate (A) water system lubricating film inorganic agent in, alkali borate Salt (A) contains lithium borate, and in alkali borate (A), lithium is 0.1~1.0 relative to the molar ratio of whole alkali metal, and alkali The molar ratio (B/M) of the boric acid B and alkali metal M of metal borate (A) are 1.5~4.0.The technology is by inhibiting due to epithelium Moisture absorption and occur epithelium crystallization, be capable of forming not only have processability, also with high corrosion-resistant epithelium.
Patent document 3 discloses a kind of non-phosphorus system's plastic processing soluble oil, which is characterized in that contains A ingredient: Inorganic system's solid lubricant, B component: wax and C ingredient: the solid mass ratio of water soluble inorganic metal salt, A ingredient and B component (A ingredient/B component) is solid quality ratio (C of 0.1~5, the C ingredient relative to the total amount of A ingredient, B component and C ingredient Ingredient/(A ingredient+B component+C ingredient)) it is 1~30%.The technology be not phosphorous lubricant, and can be realized at chemical conversion Manage the same corrosion resistance of epithelium.
Patent document 4 discloses a kind of water system lubricating film inorganic agent and its epithelium forming method, contains water-soluble inorganic Salt (A) is selected from one or more of molybdenum disulfide and graphite lubricant (B) and wax (C), and these are dispersed or dissolved in water, and (B)/ (A) with solid weight ratio meter be 1.0~5.0, (C)/(A) with solid weight ratio meter for 0.1~1.0.The technology by Cooperate molybdenum disulfide, graphite in existing water system lubricating film inorganic agent, so as to realize and the same water of chemical conversion treatment epithelium Flat high working property.
Patent document 5 discloses a kind of peel-forming agent, poly- containing silicate (A), polycarboxylate (B), water compatibility Close object and/or water compatibility biochip laminar structure (C) and molybdate and/or tungstates (D), the quality of above-mentioned each ingredient Than for requirement ratio.
As described in Patent Documents 1 to 5, water-soluble inorganic salt is the required of the solid epithelium of water system lubricating film inorganic agent Ingredient.The reason for this is that the lubricating film being made of water-soluble inorganic salt has sufficient epithelium intensity, even if in height as above Under face pressure also between mold and the interface of processed material, it is not susceptible to lubricating film disconnection, it is mutual directly to can be avoided metal Contact.Therefore, for water system lubricating film inorganic agent, by the solid skin comprising water-soluble inorganic salt, water-soluble resin Combination can reduce the suitable lubricant of coefficient of friction in film, and good lubricating status can be maintained in plastic processing.
The epithelium Forming Mechanism for the water system lubricating film being made of water soluble ingredient is illustrated.The water of water soluble ingredient Soluble inorganic salt is the state for being dissolved in water in lubricant treatment fluid, when in metal material surface application of lubricating and drying When, the water evaporation of solvent and form lubricating film.At this point, water-soluble inorganic salt is analysed in the form of solid content in metal material surface Out, solid epithelium is formed.The solid epithelium formed in this way has the epithelium intensity for being resistant to plastic processing, can be dropped by cooperation The proper lubrication agent of low-friction coefficient, to show good lubricity in plastic processing.
Existing technical literature
Patent document
Patent document 1: International Publication No. 02/012420
Patent document 2: Japanese Unexamined Patent Publication 2011-246684 bulletin
Patent document 3: Japanese Unexamined Patent Publication 2013-209625 bulletin
Patent document 4: International Publication No. 02/012419
Patent document 5: Japanese Unexamined Patent Publication 2002-363593 bulletin
Summary of the invention
Subject to be solved by the invention
But the lubricating film of Patent Documents 1 to 5 is compared with above-mentioned chemical conversion treatment epithelium, 4 months or more long-term rust preventions Property significance difference, enough could not be increased to realistic scale.The reason is that the principal component of epithelium is water soluble ingredient, therefore it is easy to inhale It receives the moisture in atmosphere or passes it through, steel readily access moisture.In patent document 2, although by inhibiting moisture absorption to be led The epithelium of cause crystallizes and improves corrosion resistance, but not inhibits moisture absorption itself, cannot obtain sufficient corrosion resistance.In addition, Patent document 3 describes: the water system lubricating film is anti-corrosion the laboratory level for accelerating to get rusty using Constant Temperature and Humidity Chambers Property test in, display and chemical conversion treatment epithelium be same or better corrosion resistance.But the environment for actually using lubricating film is usual In may adhesive dust, dust, pickling medicament mist state, status is the corrosion resistance ratioization in such harsh environment It is poor at processing epithelium.To have and chemical conversion treatment epithelium is same or better antirust in not phosphorous water system lubricating film The epithelium of property not currently exists.
In addition, as water system lubricating film than chemical conversion treatment epithelium difference a bit, the inhomogeneities of epithelium can be enumerated.Example Such as, when handling wire rod coiled material in a batch manner, when the position that overlaps each other there are wire rod, bundling position, epithelium treatment fluid without Method spreads the position, and epithelium is thinning.The thickness of epithelium has especially significant influence to corrosion resistance, therefore, occurs for example from coiled material The position tied up starts the phenomenon that getting rusty.Corrosion resistance caused by the inhomogeneities of the epithelium reduce to existing water system lubricating film and Speech is a severe project.
As the water-soluble inorganic salt obtained compared with high corrosion-resistant, the alkali metal salt that can enumerate silicate (is remembered sometimes below Carry be silicate) and tungstates alkali metal salt and/or ammonium salt (hereinafter sometimes referred to as tungstates).These water-soluble inorganics Salt is also on the books in patent document 1, patent document 4, patent document 5.But at their corrosion resistance in practical use and chemical conversion It is obvious poor compared to also to manage epithelium.
Water-soluble silicate is not easy to penetrate moisture in water-soluble inorganic salt, and has very high with the adaptation of former material Property.Although becoming due to the property not as good as chemical conversion treatment epithelium, the material compared with high corrosion-resistant can be showed.This be by In in the water volatilization of the solvent as lubricant, i.e. epithelium generating process, water-soluble silicate is crosslinked and forms grid Structure.But also just because of the network, the epithelium of water-soluble silicate was crisp as lubricating film.Therefore, exist When substrate is processed, there are epitheliums to generate cracking, is unable to fully the case where following.Moreover, because network, adaptation is excessively high, In the presence of occurring, demoulding is bad, causes the various bad situations in rear process.For example, when carrying out plating in rear process, skin Film component is mixed into plating solution and is polluted, and the part for remaining epithelium ingredient also occurs that plating is bad.
In addition, water-soluble tungstates is not easy to absorb the moisture of atmosphere when forming epithelium.This is because, water-soluble wolframic acid What is formed when salt formation epithelium is the crystallization of particle shape.In turn, water-soluble tungstates has self with the formation in metal surface The property of the passivating film of repair function can expect the formation of high corrosion-resistant epithelium by using as epithelium ingredient.In addition, This water-soluble height, therefore can easily demoulding with water system liquid.But water-soluble tungstates is crystalloid, therefore and former material Lack adaptation, and uniform epithelium can not be formed, therefore expected corrosion resistance, processability can not be obtained.For example, passing through Although synthetic resin ingredient is added in the lubricant can be improved the adaptation of epithelium, uniformity, but nonetheless corrosion resistance It is obviously poorer than chemical conversion treatment epithelium
In addition, at the water system lubricating film inorganic agent containing water-soluble inorganic salt recorded in Patent Documents 1 to 3 and chemical conversion Reason epithelium is compared, processability inequality.Especially (recorded sometimes below in the harsh processing that expanded surface area rate is decades of times or more To force work) in it is more significant, cause the deformation of former material is insufficient, die life is lower, ablation occurs etc..
By containing molybdenum disulfide, graphite, force working hour also can the water system lubricating film inorganic agent recorded in patent document 4 It is enough to obtain and chemical conversion treatment epithelium is same or better processability.But when cooperating these ingredients, the color blackening of lubricating fluid, Serious polluting device and its periphery, operating personnel.In addition, molybdenum disulfide, graphite are easy sedimentation, it is with time going by and fixed In processing trench bottom, it is difficult to redisperse sometimes, to be difficult to steadily operate.In turn, this 2 kinds of ingredients be make corrosion resistance substantially under That drops will be because not say that corrosion resistance is also poor compared with the lubricating film of Patent Documents 1 to 3 compared with chemical conversion treatment epithelium.
In patent document 5, contain silicate (A) processing of the epithelium as principal component and containing excessive anticorrodent (D) etc. Material plays ablation etc. when extrusion load is high, and poor lubricity, therefore, it is difficult to stable operations, in addition, long-term rust prevention does not also fill Point.
To which water system lubricating film can not form to have combined can be equal in real-world environment with chemical conversion treatment epithelium , high corrosion-resistant in about 4 months or more long-times and force working hour processability epithelium.Especially with regard to corrosion resistance For, epithelium is easy to become uneven, and in the thin position of film, there are problem of rustiness.In addition, containing in water system lubricating film inorganic agent When having silicate, there are the bad problems of demoulding.
Therefore, problem of the present invention is that, stringiness, pin, steel ball can be taken into account by, which providing, is thinned the processing such as draftability The corrosion proof steel wire rod and its manufacturing method with lubricating film such as property and long-term rust prevention.
Means for solving the problems
The present inventors has made intensive studies in order to solve the above problems, as a result, it has been found that, it is formed on steel wire rod aftermentioned When upper layer epithelium and lower layer's epithelium are as lubricating film, processability and corrosion resistance can be taken into account.Specifically, by being formed by zirconium Oxide and/or the epithelium that constitutes of hydroxide as lower layer's epithelium, make silicate and tungstates with specific ratios, will Tungsten/silicon mass ratio carries out and forms compound upper layer epithelium with being set as requirement ratio, to obtain individual in these ingredients In the case of the high corrosion-resistant that absolutely cannot achieve and processability.
The present invention takes following composition in order to solve the above problems.
Steel wire rod of the invention is with following purport: it is the steel wire rod with not phosphorous epithelium, and above-mentioned epithelium is from steel Wire rod side rise successively include: be made of the oxide of zirconium and/or hydroxide and film thickness be 1.0~200nm lower layer's epithelium and Containing silicon and tungsten and tungsten/silicon mass ratio 1.3~18 range upper layer epithelium.
Preferably, above-mentioned silicon comes from water-soluble silicate, and above-mentioned tungsten comes from water-soluble tungstates.
Preferably, above-mentioned silicon is from least one or more in lithium metasilicate, sodium metasilicate and potassium silicate, and above-mentioned tungsten From at least one or more in tungstate lithium, sodium tungstate, potassium tungstate and ammonium tungstate.
Preferably, resin is contained in above-mentioned upper layer epithelium, resin/(silicon+tungsten) mass ratio is 0.01~3.2.
Preferably, above-mentioned resin be selected from vinyl group resin, acrylic resin, epoxy resin, polyurethane resin, At least one or more in phenolic resin, cellulose derivative, poly and polyester resin.
Preferably, lubricant is contained in above-mentioned upper layer epithelium, lubricant/(silicon+tungsten) mass ratio is 0.01~3.2.
Preferably, above-mentioned lubricant is selected from wax, polytetrafluoroethylene (PTFE), fatty acid soaps, fatty acid metal soap, fatty acid acyl At least one or more in amine, molybdenum disulfide, tungsten disulfide, graphite and melamine cyanurate.
Preferably, the epithelium quality of the per unit area of above-mentioned upper layer epithelium is 1.0~20g/m2。
The manufacturing method of steel wire rod of the invention has following purport: making model of the steel wire rod surface contact pH 2.5~5.0 It encloses and is dissolved with the water system chemical synthesis treatment liquid of water-soluble zirconium compound and forms lower layer's epithelium.
The effect of invention
In steel wire rod of the invention, the lubricating film comprising upper layer epithelium and lower layer's epithelium takes composition as described above, Therefore the steel wire that the corrosion resistance excellents such as processabilities, the long-term rust preventions such as draftability are thinned in stringiness, pin, steel ball can be obtained Material.In addition, all same with the steel wire rod with the chemical conversion treatment epithelium or better levels of these performances, this and existing water It is lubricating film compared to being excellent.Even in particular, material overlap each other, tie up etc. it is external will water system profit because caused by In the case that sliding epithelium is thinning, high corrosion-resistant can be also obtained, this is the feature that existing water system lubricating film does not have.
Specific embodiment
The present invention be a kind of steel wire rod, which is characterized in that its be the steel wire rod with not phosphorous epithelium, above-mentioned epithelium from Steel wire rod side rise successively include: have zirconium oxide and/or hydroxide constitute and film thickness be 1~200nm lower layer's epithelium and Containing silicon and tungsten and tungsten/silicon mass ratio 1.3~18 range upper layer epithelium.
In the present invention, steel used in steel wire rod also includes carbon steel, steel alloy, special steel etc..As the steel, Ke Yilie Act carbon content be 0.2 mass % or less (not including 0 mass %) mild steel~be more than 0.2 mass % and 1.5 mass % or less a left side Right carbon steel and contained according to the purposes of carbon steel selected from silicon, manganese, phosphorus, sulphur, nickel, chromium, copper, aluminium, molybdenum, vanadium, cobalt, titanium, zircon etc. In at least one kind of steel alloy or special steel etc..In addition, steel wire rod, which refers to, usually to carry out hot-working to steel and adds in the present invention Work at wire rod product.It include steel wire in steel wire rod of the invention.Steel wire refers to: by steel wire rod wire drawing at predetermined size The product of (line footpath, circularity etc.) implements product obtained by plating processing etc. to steel to steel wire made of steel wire rod or wire drawing Wire rod has carried out the product of further processing processing.
Steel wire rod of the invention successively contains at least 2 layers of lubricating film, i.e. lower layer's epithelium and upper from the surface of steel wire rod Layer epithelium.Above-mentioned upper layer epithelium and lower layer's epithelium all can be one layer or two layers or more layer.In addition, as needed, on upper layer Other layers can also be formed on epithelium, between upper layer epithelium and lower layer's epithelium, between steel wire rod and lower layer's epithelium.
Above-mentioned epithelium is not phosphorous layer, in composition used in above-mentioned epithelium formation, without phosphorous ingredient.But It is that the ingredient in operating process etc. containing phosphorus is not precluded in the present invention and is inevitably mixed into the epithelium on steel wire rod surface The case where.That is, in actual operation, it, can be below with 1 mass % when phosphorus becomes pollutant as inevitable impurity A possibility that degree contains phosphorus, and the phosphorus leads to the brittle break of steel wire rod is low, can be considered as and phosphatizing does not occur.
Hereinafter, being successively illustrated to each ingredient of the lubricating film in steel wire rod of the invention, composition etc..
Upper layer epithelium is necessary for the epithelium containing silicon and tungsten and tungsten/silicon mass ratio in the range of 1.3~18.By with The range contains, and is capable of forming with aftermentioned silicate or tungstates individually or other water-soluble inorganic salts can not The epithelium of the high corrosion-resistant of formation, processability and sufficient adaptation.
For example, for aftermentioned water-soluble silicate and water-soluble tungstates it is compound and when forming epithelium, above-mentioned silicate institute Above-mentioned tungstates is embedded in the network of formation.As described above, the shortcomings that above-mentioned tungstates, is mainly by formation crystalline Epithelium caused by, by being embedded in the network of above-mentioned silicate, above-mentioned tungstates can be in uniform and fine mode In the presence of.To, have both above-mentioned silicate make the not meable property of moisture and above-mentioned tungstates have the function of self-regeneration Passivating film, corrosion resistance significantly improves.
In addition, the influence as above-mentioned tungstates to above-mentioned silicate, can enumerate the improvement of demoulding.As described above, The processability of above-mentioned silicate, the reason of demoulding difference are that above-mentioned silicate is formd by producing high-molecular firmly to be connected Continuous epithelium, the above-mentioned tungstates of combined state is in the network of above-mentioned silicate, to appropriately suppressed firm The formation of network can be improved processability, demoulding.
Tungsten/silicon mass ratio preferably 1.3 or more, preferably 1.8 or more, more preferable 2.0 or more.The mass ratio preferably 18 with Under, preferably 10 or less, more preferable 5.4 or less.
When tungsten/silicon mass ratio is lower than 1.3, other than it can not obtain sufficient corrosion resistance, processability, also it will become de- The epithelium of film property difference.The reason is that since opposite reduce of the amount of above-mentioned tungstates forms passivating film with being unable to fully；Above-mentioned silicon When hydrochlorate amount relative increase, firm network will form.When tungsten/silicon mass ratio is more than 18, will become can not be filled The epithelium of the corrosion resistance, processability divided.The reason is that moisture readily penetrates through, above-mentioned tungstates when silicate amount is reduced relatively Crystallization be precipitated, the adaptation of epithelium, uniformity reduce.It should be noted that in the present invention, tungsten/silicon mass ratio is preferably The ratio of wolfram element based on the water-soluble tungstates in epithelium and the element silicon from water-soluble silicate, can be according to Aftermentioned mode calculates.
Lower layer's epithelium is made of the oxide of zirconium and/or hydroxide, preferably the oxide of zirconium.In the present invention, lower layer's skin Film is sometimes referred to as zirconium epithelium.
The film thickness of lower layer's epithelium is 1.0nm or more, preferably 5nm or more, more preferable 20nm or more.In addition, above-mentioned film thickness is 200nm is hereinafter, it is preferred that 150nm or less, more preferable 130nm or less.When film thickness is less than 1.0nm, zirconium epithelium is become too thin, Wu Fafa Wave sufficient corrosion resistance.And film thickness be greater than 200nm when, corrosion resistance is not influenced, but occur epithelium closely sealed bad, processability Decline.
By so forming zirconium epithelium, corrosion resistance can be improved.This is because, by additional zirconium epithelium as lower layer's skin Film not only in conjunction with being reinforced, and has in conjunction with strengthening section so that the network of above-mentioned silicate changes due to zirconium epithelium Moisture blocking ability, therefore corrosion resistance further increases.In addition, zirconium epithelium is very thin compared with the epithelium of upper layer, even therefore Common water system lubricating film is easy thinning position, is easily formed uniform epithelium, even if in such position, corrosion resistance Also it improves.In turn, for as described previously for corrosion resistance is improved, the network of upper layer epithelium and the combination of zirconium epithelium are strengthened Portion is important, therefore is also not susceptible to the influence of upper layer epithelium entirety film thickness.Therefore, even above-mentioned water system lubricating film It is easy thinning position, can also give full play to corrosion resistance.In the case where individual zirconium epithelium, epithelium generates defect, becomes rotten Starting point is lost, processing performance can not be obtained, therefore become bad.
To by combining the epithelium of above-mentioned silicate and above-mentioned tungstates with zirconium epithelium, so as to realize before this The high corrosion-resistant in high working property and real-world environment that can not be shown.
Preferred above-mentioned silicon comes from water-soluble silicate in the present invention, and above-mentioned tungsten comes from water-soluble tungstates.
The type of above-mentioned water-soluble silicate can enumerate such as sodium metasilicate, potassium silicate, lithium metasilicate, ammonium silicate.These can To be used alone, two or more can also be combined.
The type of above-mentioned water solubility tungstates can enumerate such as sodium tungstate, potassium tungstate, tungstate lithium, ammonium tungstate.These can To be used alone, two or more can also be combined.
As the zirconium supply source in the epithelium inorganic agent for being used to form zirconium epithelium according to the present invention, can enumerate for example Zirconium sulfate, zirconium oxysulfate, zirconium sulfate ammonium, zirconium nitrate, zirconyl nitrate, zirconium nitrate ammonium, zirconium acetate, zirconium lactate, zirconium chloride, fluorine zirconium Acid, fluorine zirconium complex salt etc..These can be used alone, and can also combine two or more.
Then resin is illustrated.Resin is made for cementation, the adaptation of raising substrate and epithelium, based on thickening With and assign levelability, dispersion component stabilized purpose and cooperate in the epithelium of upper layer.
Resin with such function and property can enumerate vinyl group resin, acrylic resin, epoxy resin, Polyurethane resin, phenolic resin, cellulose derivative, poly, polyester resin.These can be used alone, can also be by 2 Kind combination of the above.
In the present invention, resin is contained in above-mentioned upper layer epithelium, resin/(silicon+tungsten) mass ratio preferably 0.01 or more is more excellent Select 0.1 or more.In addition, above-mentioned mass ratio preferably 3.2 is hereinafter, more preferable 2.1 or less.When less than 0.01, it cannot give full play to Effect is stated, when more than 3.2, the amount of silicon and tungsten is opposite to tail off, and can not show the high corrosion-resistant and processability as feature of present invention.
Then lubricant is illustrated.Lubricant itself has sliding property, has the function of reducing frictional force.It is logical Often, if frictional force increases in plastic processing, increase, heat release, ablation of power consumption of polymer processing etc. occurs, when steel wire rod of the invention Upper layer epithelium in contain lubricant when, exist in lubricating film with solid forms, inhibit the increase of frictional force.With in this way Function and the lubricant of property can enumerate wax, polytetrafluoroethylene (PTFE), fatty acid soaps, fatty acid metal soap, fatty acid amide, two Molybdenum sulfide, tungsten disulfide, graphite, melamine cyanurate.These can be used alone, and can also combine two or more.
As the concrete example of wax, polyethylene wax, olefin wax, microwax, polypropylene wax, Brazil wax can be enumerated.Make For the concrete example of fatty acid soaps, can enumerate Sodium myristate, potassium myristate, sodium palmitate, potassium palmitate, odium stearate, Potassium stearate.As the concrete example of fatty acid metal soap, calcium stearate, zinc stearate, barium stearate, stearic acid can be enumerated Magnesium, lithium stearate.Fatty acid amide is that the amide compound for example with 2 fatty acid can enumerate sub- second as concrete example Base dilaurate amide, ethylenebis stearic amide, ethylenebis behenamide, N, the hard ester group adipic acid acyl of N '-two Amine, ethylenebisoleaamide, ethylenebis erucyl amide, hexamethylene bis oleamide, N, N '-dioleoyl adipic acid Amide.
In the present invention, contain lubricant in above-mentioned upper layer epithelium, lubricant/(silicon+tungsten) mass ratio preferably 0.01 or more, More preferable 0.1 or more, the mass ratio preferably 3.2 is hereinafter, more preferable 2.1 or less.Here, lubricant/(silicon+tungsten) mass ratio is small When 0.01, lubricant is very few, therefore cannot play above-mentioned performance.When more than 3.2, the amount of silicon and tungsten is opposite to tail off, Wu Fabiao Now as the high corrosion-resistant of feature of present invention and processability.
In order to ensure state, the upper layer of steel wire rod of the invention are uniformly coated with when application of lubricating treatment fluid on substrate Epithelium, can also be for imparting levelability and the cooperation viscosity adjustment of thixotropic purpose other than silicon, tungsten, resin, lubricant Agent.As the concrete example of such viscosity modifier, can enumerate montmorillonite, sauconite, beidellite, hectorite, nontronite, Montmorillonites system clay mineral and the fine particle silicas, swelling such as saponite, griffithite (Ferrosaponite) and magnesium-rich smectite Inorganic system's tackifier such as soil, kaolin.
In order to improve adaptation, processability, above-mentioned upper layer epithelium can also contain the inorganic salts such as sulfate, borate, have The water soluble salts such as machine salt.As sulfate, sodium sulphate, potassium sulfate etc. can be enumerated.As borate, metaboric acid can be enumerated Sodium, potassium metaborate, ammonium metaborate etc..
As organic salt, formic acid, acetic acid, butyric acid, oxalic acid, succinic acid, lactic acid, ascorbic acid, tartaric acid, lemon can be enumerated The salt with alkali metal, alkaline-earth metal etc. such as lemon acid, malic acid, malonic acid, maleic acid, phthalic acid.
The epithelium of steel wire rod of the invention can assign high corrosion-resistant afterwards before processing, corrosion proof for further increasing Purpose can also cooperate other water soluble anti-rust agents, inhibitor.As concrete example, can be used oleic acid, dimeric dibasic acid, tartaric acid, The various organic acids such as citric acid, the various chelating agents such as EDTA, NTA, HEDTA, DTPA, the alkanolamines such as triethanolamine are mixed into Point；And amine salt of p-tert-butyl benzoic acid etc., the amine salt of carboxylic acid, 2 yuan of sour amine salt, alkenyl succinic acid and its water soluble salt With Aminotetrazole and its water soluble salt and with etc. well known to substance.It, can also be with it should be noted that these can be used alone It combines two or more.
Upper layer epithelium inorganic agent used in the present invention contains above-mentioned water-soluble silicate, above-mentioned water-soluble tungstates conduct Essential component contains above-mentioned resin, above-mentioned lubricant, above-mentioned water soluble salt as needed.
Above-mentioned water-soluble silicate is preferably in 100 mass % of upper layer epithelium inorganic agent more than 5 mass %, more preferable 10 matter Measure % or more, and then preferably 15 mass % or more；It is preferred that 58 mass % hereinafter, more preferable 52 mass % hereinafter, in turn preferably 45 Quality % or less.
Above-mentioned water solubility tungstates is 10 mass % or more preferably in 100 mass % of upper layer epithelium inorganic agent, more preferably 15 mass % or more, and then preferably 20 mass % or more；It is preferred that 91 mass % hereinafter, more preferable 85 mass % hereinafter, excellent in turn Select 80 mass % or less.
The amount of above-mentioned water-soluble silicate is 5 mass % or less, the amount of above-mentioned water-soluble tungstates is more than 91 mass % When, sufficient long-term rust prevention can not be obtained, and become the epithelium of the thinned draftability difference of stringiness, steel ball.The reason is that Since water-soluble silicate amount becomes relatively rarely, moisture becomes easy transmission, is precipitated the crystallization of tungsten, the adaptation of epithelium, uniformly Property reduce.
The amount of above-mentioned water-soluble silicate be more than the amount of 58 mass %, above-mentioned water-soluble tungstates less than 10 mass % when, Become can not to obtain the epithelium of sufficient corrosion resistance, processability.The reason is that reducing by the way that tungsten amount is opposite, it is unable to fully shape At passivating film, water-soluble silicate amount relative increase, so as to form firm network.
The substrate lubricating film that lower layer's epithelium of steel wire rod of the invention can be used as dry lube uses.Pass through work It is used for the substrate epithelium of dry lube, so as to promote lubricity, ablation resistance, corrosion resistance.To dry lube Type is not particularly limited, can be used such as with higher fatty acids soap, borax, lime, molybdenum disulfide for the normal of principal component See powdered lubricant, wire drawing powder.
In the present invention, the liquid medium (solvent, decentralized medium) in upper layer epithelium inorganic agent and zirconium epithelium inorganic agent is water. It, can be in order to shorten the drying time of lubricant in drying process it should be noted that for the epithelium inorganic agent of upper layer The alcohol for cooperating boiling point lower than water.
In above-mentioned upper layer epithelium inorganic agent, in order to improve the stability of liquid, water-soluble highly basic ingredient can be contained.Make For concrete example, lithium hydroxide, sodium hydroxide, potassium hydroxide can be enumerated.These can be used alone, can also be by two or more Combination.These use level is relative to solid gross mass preferably 0.01~10 mass %.
Then the manufacturing method of steel wire rod of the invention is illustrated.The method of the present invention includes cleaning for steel wire rod Process, the upper layer epithelium inorganic agent as water system lubricating film inorganic agent and lower layer's epithelium inorganic agent (water system chemical synthesis treatment liquid) Manufacturing process and drying process.Each process is illustrated below.
< cleans process (pretreatment procedure) >
Before forming epithelium on steel wire rod, preferably carries out selected from shot-peening, sandblasting, squirts, removes, in alkali degreasing and pickling At least one cleaning treatment.Cleaning here is referred to remove the oxide skin, the various spots that are grown due to annealing etc. The operation of (oil etc.).
The manufacturing process > of < zirconium epithelium
Above-mentioned lower layer's epithelium make steel wire rod surface and pH 2.5~5.0 range and dissolved with water-soluble zirconium compound Water system chemical synthesis treatment liquid is contacted and is formed.Above-mentioned water system chemical synthesis treatment liquid can be the treatment fluid containing above-mentioned zirconium supply source.pH It is preferred that 2.8~4.8, more preferable 3.1~4.6, further preferred 3.4~4.4.When pH is less than 2.5, etching is excessive, not only epithelium Precipitation efficiency reduce, and have interfere epithelium the anxiety being formed uniformly.When pH is more than 5.0, liquid stability reduce, be precipitated compared with More zirconium compounds or slurry has the anxiety for being formed to epithelium and generating adverse effect.
Above-mentioned water system chemical synthesis treatment liquid can be commercially available zirconium chemical conversion treatment agent, zirconium concentration (quality criteria) preferred 10ppm Above, more preferable 30ppm or more, preferably 500ppm or less, more preferable 300ppm or less.
In the present invention, the contact method for being used to form zirconium epithelium is not particularly limited, can enumerate such as spraying treatment, Impregnation, flushing processing.In order to promote the formation of epithelium, temperature, the treatment temperature of water system chemical synthesis treatment liquid when contact It is preferred that 20~60 DEG C, more preferable 30~50 DEG C.In addition, time of contact also depends on the material, structure, chemical synthesis treatment liquid of steel wire rod Concentration, treatment temperature, but preferably approximately 2~600 seconds or so, can suitably be adjusted according to epithelium amount.After chemical conversion treatment preferably Washing step is set, so that the water system chemical synthesis treatment liquid for being attached to steel will not enter in the epithelium treatment fluid of upper layer.
The manufacturing process > of the upper layer < epithelium
Then, upper layer epithelium is formed on the zirconium epithelium obtained in the manner described above.Steel is used for by above-mentioned upper layer epithelium The process of wire rod is not particularly limited, and the coating methods such as infusion process, flow coat method, spray-on process can be used.For coating, as long as Surface is sufficiently by the upper layer epithelium inorganic agent covering as water system lubricating film inorganic agent, to coating duration also without special Limitation.Here, it in order to improve drying property at this time, is handled after steel wire rod being heated to 60~80 DEG C with water system lubricating film Agent contact.In addition it is also possible to be contacted with the water system lubricating film inorganic agent for being heated to 40~70 DEG C.To which drying property substantially mentions Height is also able to carry out drying at normal temperature sometimes, additionally it is possible to reduce the loss of thermal energy.
< drying process >
It is then necessary to which upper layer epithelium inorganic agent is dried.Drying can be room temperature, can also be 60~150 DEG C carry out 1~30 minute.
Here, the epithelium quality for being formed in the upper layer epithelium on steel wire rod surface needs to suitably refer to processing stage hereafter, The preferred 1.0g/m of epithelium quality2Above, more preferable 2.0g/m2More than；It is preferred that 20g/m2Below, more preferably 15g/m2Below.At this When epithelium quality is few, lubricity is become inadequate.In addition, being more than 20g/m in epithelium quality2When, although there is no problem for lubricity, But dregs blocking mold can be caused etc., so not preferably.It should be noted that epithelium quality can pass through steel wire before and after the processing The of poor quality and surface area of material and calculate.In order to carry out referring to and reach above-mentioned epithelium mass range, and to water system lubricating film The solid quality (concentration) of inorganic agent is suitably adjusted.In fact, being by the lubricant water of high concentration in most cases Dilution, come in the form of the treatment fluid using.The water for being diluted adjustment is not particularly limited, such as pure water can be used, go Ionized water, tap water, underground water, industrial water etc..
< method for demoulding >
In the present invention, upper layer epithelium can be by being impregnated in water-based alkalis or by jet cleaning demoulding.Alkali Detergent is the liquid in water dissolved with general alkali compositions such as sodium hydroxide, potassium hydroxide, is in contact with it upper layer epithelium When, upper layer epithelium is dissolved in cleaning solution, therefore can easily demoulding.In addition, forming the heat treatment being easy by after processing And exuviae film.Therefore, the pollution of process, plating are bad in not after capable of preventing caused by demoulding is bad in neutralizing treatment So.
Then the analysis method of epithelium composition is illustrated.
As the analysis method of zirconium epithelium, can enumerate at section SEM (Scanning Electron Microscope) The method of leather film thickness is directly observed in observation or sectional tem (Transmission Electron Microscope) observation. At this point, passing through CP (Cross-section Polisher) processing, FIB to observe section under conditions of not damaging epithelium The method of (Focused Ion Beam) processing and fabricating section is effective.Briefly, it can enumerate and use x-ray fluorescence analysis The method that (XRF:X-ray Fluorescence) analyzes the zirconium film thickness of steel surface.At this point, upper layer epithelium is preferred It is removed in advance with alkaline aqueous solution etc..For the film thickness measuring of lower layer's epithelium, steel surface after having removed upper layer epithelium, The region for randomly choosing 3 progress film thickness measuring carries out film thickness measuring to the whole of the selection region.Then, by 3 positions Film thickness of the average value of the thickness measured as the substrate epithelium of steel.
As upper layer epithelium composition analysis method, can enumerate for example using induced-coupled plasma body (ICP: Inductively Coupled Plasma) method.At this point it is possible to which the epithelium on steel is dissolved in strong alkaline aqueous solution Deng measuring the amount of lysed silicon and tungsten with ICP, analyzed so as to the composition to epithelium.
In addition, when being difficult to dissolve upper layer epithelium, it can also be by utilizing x-ray fluorescence analysis (XRF:X-ray Fluorescence) method that the amount of the silicon to steel wire rod surface and tungsten is directly analyzed carries out the analysis of epithelium composition.
Embodiment
Hereinafter, embodiment will be enumerated together with comparative example, to using the case where steel wire rod is as object and of the invention Effect is further illustrated.It should be noted that the present invention is not limited by these embodiments.Hereinafter, as long as no Special declaration, then " part " expression " mass parts ", " % " expression " quality % ".
The manufacture of (1-1) as the upper layer epithelium inorganic agent and lower layer's epithelium inorganic agent of water system lubricating film inorganic agent
By each ingredient as shown below according to combination shown in table 1 and ratio preparation embodiment 1~12 and comparative example 2~17 Upper layer epithelium inorganic agent and lower layer's epithelium inorganic agent as water system lubricating film inorganic agent.Embodiment 1~12 and comparative example 3~ In 17 upper layer epithelium inorganic agent, in order to improve liquid stability, lithium hydroxide joined with 1% concentration in a liquid.It needs It is noted that comparative example 18 is phosphate/soap processing, wire drawing powder is not used.
A. upper layer epithelium inorganic agent
< water-soluble silicate >
(A-1) sodium metasilicate
(A-2) No. 3 sodium metasilicate (Na2O·nSiO2N=3)
(A-3) lithium metasilicate (Li2O·nSiO2N=3.5)
< water solubility tungstates >
(B -1) ammonium tungstate
(B-2) sodium tungstate
(B-3) potassium tungstate
< resin >
(C-1) polyvinyl alcohol (average molecular weight about 50,000)
(C-2) in the sodium of isobutylene maleic acid anhydride copolymer and salt (average molecular weight about 165,000)
< lubricant >
(D-1) polyethylene wax (5 μm of average grain diameter)
(D-2) ethylenebis stearic amide
< water soluble salt >
(E-1) kodalk
(E-2) sodium tartrate
(E-3) sodium sulphate
(E-4) sodium pyrophosphate
B. lower layer's epithelium inorganic agent
< zirconium lower layer epithelium >
(F) zirconium chemical conversion treatment agent (パ ル シ ー De (registered trademark) 1500, Nihon Parkerizing Co., Ltd. System)
Lower layer epithelium > other than < zirconium lower layer epithelium
(G-1) No. 2 sodium metasilicate (Na2O·nSiO2N=2.5)
(G-2) trbasic zinc phosphate
[table 1]
(A)~(E) number shown in ingredient is additive amount (quality %) in the epithelium inorganic agent of upper layer
The analysis of (1-2) epithelium
The formation processing of lower layer's epithelium and upper layer epithelium will be implementedTest material be heated to 60 DEG C 2% sodium hydrate aqueous solution in impregnate 2 minutes, upper layer epithelium is removed.Then, pass through induced-coupled plasma body (ICP) amount of silicon and tungsten contained in sodium hydrate aqueous solution used in measurement removing, investigates the value of tungsten/silicon mass ratio. Then, it is impregnated 2 minutes in 2% sodium hydrate aqueous solution for being heated to 60 DEG C, extra upper layer epithelium is removed.To removing The test material of upper layer clad implements x-ray fluorescence analysis (XRF), to measure the film thickness of zirconium epithelium.Measured value such as 1 institute of table Show.In addition, measuring the thickness of lower layer's epithelium by implementing section sem analysis, film thickness is measured.In the film thickness measuring, with regard under Layer epithelium (i.e. zirconium epithelium) film thickness measurement for, removed the steel after the epithelium of upper layer surface random selection 3 at into The region of row film thickness measuring carries out film thickness measuring in the whole of the selection region.Then, by the thickness of 3 position finding Film thickness of the average value as the substrate epithelium of steel.
The processing of (1-3) epithelium
Epithelium processing method described below.It should be noted that material processed isSteel wire rod, in order to reproduce The filming of the lubricating film of tie part, to be tied up the state that band is tied up with plastic and handled.
The pre-treatment of < embodiment 1~12 and comparative example 3~15 and epithelium handle >
(a) degreasing: commercially available degreasing agent (Fine Cleaner (registered trademark) 6400, Nihon Parkerizing Co., Ltd. system) concentration 20g/L, temperature 60 C, dipping 10 minutes
(b) it washes: tap water, room temperature, dipping 30 seconds
(c) pickling: hydrochloric acid, concentration 17.5%, room temperature, dipping 10 minutes
(d) it washes: tap water, room temperature, dipping 30 seconds
(e) lower layer's epithelium is handled: commercially available zirconium chemical conversion treatment agent (パ ル シ ー De (registered trademark) 1500, Nihon Parkerizing Co., Ltd. system), concentration 50g/L, temperature 45 C, pH4.0 impregnation dip time according to epithelium amount and Appropriate adjustment
(f) it washes: tap water, room temperature, dipping 30 seconds
(g) upper layer epithelium is handled: upper layer epithelium inorganic agent, temperature 60 C, the dipping manufactured in (1-1) 1 minute
(h) dry: 100 DEG C, 10 minutes
The pre-treatment of < comparative example 1 and epithelium handle >
(a) degreasing: commercially available degreasing agent (Fine Cleaner (registered trademark) 6400, Nihon Parkerizing Co., Ltd. system) concentration 20g/L, temperature 60 C, dipping 10 minutes
(b) it washes: tap water, room temperature, dipping 30 seconds
(c) pickling: hydrochloric acid, concentration 17.5%, room temperature, dipping 10 minutes
(d) it washes: tap water, room temperature, dipping 30 seconds
(e) pure water is washed: deionized water, room temperature, 30 DEG C of dipping
(f) dry: 100 DEG C, 10 minutes
The pre-treatment of < comparative example 2 and epithelium handle >
(a) degreasing: commercially available degreasing agent (Fine Cleaner (registered trademark) 6400, Nihon Parkerizing Co., Ltd. system) concentration 20g/L, temperature 60 C, dipping 10 minutes
(b) it washes: tap water, room temperature, dipping 30 seconds
(c) pickling: hydrochloric acid, concentration 17.5%, room temperature, dipping 10 minutes
(d) it washes: tap water, room temperature, dipping 30 seconds
(e) lower layer's epithelium is handled: commercially available zirconium chemical conversion treatment agent (パ ル シ ー De (registered trademark) 1500, Nihon Parkerizing Co., Ltd. system) concentration 50g/L, temperature 45 C, pH4.0 impregnation dip time fit according to epithelium amount Work as adjustment
(f) it washes: tap water, room temperature, 30 DEG C of dipping
(g) pure water is washed: deionized water, room temperature, 30 DEG C of dipping
(h) dry: 100 DEG C, 10 minutes
< comparative example 16 (silicate lower layer epithelium, the processing of upper layer epithelium) >
(a) degreasing: commercially available degreasing agent (Fine Cleaner (registered trademark) 6400, Nihon Parkerizing Co., Ltd. system) concentration 20g/L, temperature 60 C, dipping 10 minutes
(b) it washes: tap water, room temperature, dipping 30 seconds
(c) pickling: hydrochloric acid, concentration 17.5%, room temperature, dipping 10 minutes
(d) it washes: tap water, room temperature, dipping 30 seconds
(e) lower layer's epithelium is handled: commercially available substrate treating agent (プ レ パ レ Application (registered trademark) 5557, Nihon Parkerizing Co., Ltd. system) concentration 2.5g/L, temperature 70 C, dipping 1 minute
(f) thick dry: room temperature, 60 seconds
(g) upper layer epithelium is handled: upper layer epithelium inorganic agent temperature 60 C, the dipping manufactured in (1-1) 1 minute
(h) dry: 100 DEG C, 10 minutes
The pre-treatment of < comparative example 17 (trbasic zinc phosphate lower layer epithelium, the processing of upper layer epithelium) and epithelium handle >
(a) degreasing: commercially available degreasing agent (Fine Cleaner (registered trademark) 6400, Nihon Parkerizing Co., Ltd. system) concentration 20g/L, temperature 60 C, dipping 10 minutes
(b) it washes: tap water, room temperature, dipping 30 seconds
(c) pickling: hydrochloric acid, concentration 17.5%, room temperature, dipping 10 minutes
(d) it washes: tap water, room temperature, dipping 30 seconds
(e) lower layer's epithelium is handled: commercially available trbasic zinc phosphate chemical conversion treatment agent (パ Le ボ Application De (registered trademark) 3696X, Nihon Parkerizing Co., Ltd. system) concentration 75g/L, 80 DEG C of temperature, dipping 10 minutes
(f) it washes: tap water, room temperature, dipping 30 seconds
(g) upper layer epithelium is handled: upper layer epithelium inorganic agent temperature 60 C, the dipping manufactured in (1-1) 1 minute
(h) dry: 100 DEG C, 10 minutes
The pre-treatment of < comparative example 18 (phosphate/soap processing) and epithelium handle >
(a) degreasing: commercially available degreasing agent (Fine Cleaner (registered trademark) 6400, Nihon Parkerizing Co., Ltd. system) concentration 20g/L, temperature 60 C, dipping 10 minutes
(b) it washes: tap water, room temperature, dipping 30 seconds
(c) pickling: hydrochloric acid, concentration 17.5%, room temperature, dipping 10 minutes
(d) it washes: tap water, room temperature, dipping 30 seconds
(e) chemical conversion treatment: commercially available trbasic zinc phosphate chemical conversion treatment agent (パ Le ボ Application De (registered trademark) 3696X, Nihon Parkerizing Co., Ltd. system) concentration 75g/L, 80 DEG C of temperature, dipping 10 minutes
(f) it washes: tap water, room temperature, dipping 30 seconds
(g) soap is handled: commercially available reaction soap lubricant (パ ル ー Block (registered trademark) 235, Nihon Parkerizing Co., Ltd. system) concentration 70g/L, 85 DEG C of temperature, 3 points of dipping
(h) dry: 100 DEG C, 10 minutes
(i) dry epithelium amount: 10g/m2
(1-4) evaluation test
(1-4-1) processability (stringiness) test
Pass throughMold pairTest material carry out drawing to carrying out wire drawing.As Dry lube uses the ミ サ イ Le C40 of loose Pu industrial (strain).Material will carried out being put into the mold box before drawing Dry lube is attached to it on material naturally.By after wire drawing test material ablation and lubricating film remaining quantity into Row evaluation.
Evaluation criteria
◎: without ablation, metallic luster is had no.More epithelium has been remained on the whole.
Zero: no ablation also has no metallic luster, but remaining epithelium ratio ◎ is slightly few.
△: without ablation but epithelium remaining quantity it is slightly few, the visible metallic luster of portion.
▲: without ablation but in metallic luster visible compared with multiposition.
×: ablation occurs.
(1-4-2) corrosion resistance (long-term rust prevention) test
The wire rod for having carried out above-mentioned stringiness test is exposed 2 weeks or 4 months in open environment in doors in summer, is seen Examine situation of getting rusty.The rust area the big, is judged as that corrosion resistance is poorer.
Evaluation criteria
◎: significantly excellent compared with phosphate/soap bark film (rust area is less than 5%)
Zero: excellent compared with phosphate/soap bark film (rust area is 5% more than and less than 15%)
△: being same (rust area is 15% more than and less than 25%) with phosphate/soap bark film
▲: (rust area is 25% more than and less than 35%) poorer than phosphate/soap bark film
×: significance difference compared with phosphate/soap bark film (rust area is 35% or more)
Test result is as shown in table 2.Embodiment has remained more epithelium, and processability is good, and corrosion resistance is also good As a result.Comparative example 1 is without using the level with upper layer epithelium of the invention same and lower layer's epithelium, and ablation occurs for when wire drawing.Than It is the test level in the case where only zirconium epithelium compared with example 2, ablation equally occurs with comparative example 1, therefore processability is insufficient, it is anti-corrosion Property is also insufficient.Comparative example 3,4 be by the film thickness of zirconium epithelium out of the range of the present invention in a manner of come using example.Zirconium epithelium The excessively thin comparative example 3 of film thickness in, corrosion resistance reduces, and in the blocked up comparative example 4 of the film thickness of zirconium epithelium, has what processability reduced to incline To.Comparative example 5~12 is the example by the setting of the quality ratio of silicon and tungsten out of the range of the present invention, the epithelium remaining after wire drawing Amount is few, therefore poor in processability, corrosion resistance are also poor.Comparative example 13~15 is containing other than water-soluble silicate, water-soluble tungstates Example of the ingredient as water-soluble inorganic salt, the epithelium remaining quantity after wire drawing is few, therefore poor in processability, corrosion resistance are also poor.Than It is example of the epithelium as lower layer's epithelium for being coated with water-soluble silicate compared with example 16, can not obtains as the embodiment high anti-corrosion Property.Comparative example 17 is the example to form phosphatic epithelium as lower layer's epithelium.Processability, corrosion resistance and embodiment are same water It is flat, but since the epithelium contains phosphorus, there are the phosphatizings such as bolt as described above, therefore not preferably.Comparative example 18 To phosphate coating carried out reaction soap processing example the phosphatizings problem such as bolt, phosphate are also equally existed with comparative example 17 Epithelium is undesirable.It is similarly deposited as shown in comparative example 12,13 when containing phosphate as water soluble salt about phosphatizing ?.
In addition, material is tied up with bundling belt each other, tie up partial stream lubricating film it is thinning in the case where, can also assign Give high corrosion-resistant.
[table 2]
※ 1 zero: not phosphorous, a possibility that there is no the brittle breaks of the steel wire rod as caused by phosphorus
×: containing phosphorus, there is a possibility that brittle break of the steel wire rod as caused by phosphorus
By enumerating the embodiment using steel wire as object together with comparative example, carried out together with to effect of the invention more into One step illustrates.It should be noted that the present invention is not limited by these embodiments.Hereinafter, as long as no special declaration, then " part " refers to that " mass parts ", " % " refer to " quality % ".
The manufacture of (2-1) as the upper layer epithelium inorganic agent object and lower layer's epithelium inorganic agent of water system lubricating film inorganic agent
Each ingredient as shown below is prepared into embodiment 13~29 and comparative example 19 according to combination shown in table 3 and ratio ~35 upper layer epithelium inorganic agent and lower layer's epithelium inorganic agent.It should be noted that comparative example 36 is phosphate/soap processing.
A. upper layer epithelium inorganic agent
< water-soluble silicate >
(A-1) sodium metasilicate
(A-2) No. 3 sodium metasilicate (Na2O·nSiO2N=3)
(A-3) lithium metasilicate (Li2O·nSiO2N=3.5)
< water solubility tungstates >
(B -1) ammonium tungstate
(B-2) sodium tungstate
(B-3) potassium tungstate
< resin >
(C-1) polyvinyl alcohol (average molecular weight about 50,000)
(C-2) in the sodium of isobutylene maleic acid anhydride copolymer and salt (average molecular weight about 165,000)
(C-3) sodium carboxymethylcellulose (average molecular weight about 30,000)
(C-4) water system nonionic ester-polyurethane resin emulsion
< lubricant >
(D-1) anionic property polyethylene wax (5 μm of average grain diameter)
(D-2) ethylenebis stearic amide
(D-3) calcium stearate
(D-4) polytetrafluoroethyldispersion dispersion (0.2 μm of average grain diameter)
< water soluble salt >
(E-1) kodalk
(E-2) sodium tartrate
(E-3) sodium sulphate
(E-4) sodium pyrophosphate
B. lower layer's epithelium inorganic agent
< zirconium lower layer epithelium >
(F) zirconium chemical conversion treatment agent (パ ル シ ー De (registered trademark) 1500, Nihon Parkerizing Co., Ltd. System)
Lower layer epithelium > other than < zirconium lower layer epithelium
(G-1) No. 2 sodium metasilicate (Na2O·nSiO2N=2.5)
(G-2) trbasic zinc phosphate
[table 3]
(A)~(E) additive amount (quality) in number shown in ingredient is at above-mentioned epithelium in agent-
The analysis of (2-2) epithelium
The formation processing that lower layer's epithelium and upper layer epithelium are carried out to SPCC-SD material, directly passes through x-ray fluorescence analysis (XRF) silicon on surface and the amount of tungsten are measured, the value of tungsten/silicon mass ratio is investigated.Then, it is being heated to 60 DEG C of 2% hydrogen-oxygen Change and impregnated 2 minutes in sodium water solution, upper layer epithelium is removed.Fluorescent X-ray point is implemented to the test material for having removed upper layer epithelium It analyses (XRF), to measure the film thickness of zirconium epithelium.Measured value is recorded in table 3.By the film thickness of XRF measurement and by implementing section SEM The result analyzed and directly measure zirconium leather film thickness is consistent.
The processing of (2-3) epithelium
The pre-treatment of < embodiment 13~29 and comparative example 20~33 and epithelium handle >
(a) degreasing: commercially available degreasing agent (Fine Cleaner (registered trademark) E6400, Nihon Parkerizing Co., Ltd. system) concentration 20g/L, temperature 60 C, dipping 10 minutes
(b) it washes: tap water, room temperature, dipping 20 seconds
(c) pickling: 17.5% hydrochloric acid, room temperature, dipping 20 minutes
(d) it washes: tap water, room temperature, dipping 20 seconds
(e) lower layer's epithelium is handled: commercially available zirconium chemical conversion treatment agent (パ ル シ ー De (registered trademark) 1500, Nihon Parkerizing Co., Ltd. system) concentration 50g/L, temperature 45 C, pH4.0 impregnation dip time fit according to epithelium amount Work as adjustment
(f) it washes: tap water, room temperature, dipping 20 seconds
(g) it neutralizes: commercially available neutralizer (プ レ パ レ Application (registered trademark) 27, Nihon Parkerizing Co., Ltd. it makes)
(h) upper layer epithelium is handled: upper layer epithelium inorganic agent, temperature 60 C, the dipping manufactured in (2-1) 1 minute
(i) dry: 100 DEG C, 10 minutes
The pre-treatment of < comparative example 19 and epithelium handle >
(a) degreasing: commercially available degreasing agent (Fine Cleaner (registered trademark) 6400, Nihon Parkerizing Co., Ltd. system) concentration 20g/L, temperature 60 C, dipping 10 minutes
(b) it washes: tap water, room temperature, dipping 30 seconds
(c) pickling: concentration of hydrochloric acid 17.5%, room temperature, dipping 10 minutes
(d) it washes: tap water, room temperature, dipping 30 seconds
(e) lower layer's epithelium is handled: commercially available zirconium chemical conversion treatment agent (パ ル シ ー De (registered trademark) 1500, Nihon Parkerizing Co., Ltd. system) concentration 50g/L, temperature 45 C, pH4.0, impregnation, dip time according to epithelium amount and Appropriate adjustment
(f) it washes: tap water, room temperature, 30 DEG C of dipping
(g) pure water is washed: deionized water, room temperature, 30 DEG C of dipping
(h) dry: 100 DEG C, 10 minutes
< comparative example 34 (silicate lower layer epithelium, the processing of upper layer epithelium) >
(a) degreasing: commercially available degreasing agent (Fine Cleaner (registered trademark) 6400, Nihon Parkerizing Co., Ltd. system) concentration 20g/L, temperature 60 C, dipping 10 minutes
(b) it washes: tap water, room temperature, dipping 30 seconds
(c) pickling: hydrochloric acid, concentration 17.5%, room temperature, dipping 10 minutes
(d) it washes: tap water, room temperature, dipping 30 seconds
(e) lower layer's epithelium is handled: commercially available substrate treating agent (プ レ パ レ Application (registered trademark) 5557, Nihon Parkerizing Co., Ltd. system) concentration 2.5g/L, temperature 70 C, dipping 1 minute
(f) thick dry: room temperature, 60 seconds
(g) upper layer epithelium is handled: upper layer epithelium inorganic agent, temperature 60 C, the dipping 1 minute (h) manufactured in (2-1) is dry It is dry: 100 DEG C, 10 minutes
The pre-treatment of < comparative example 35 (trbasic zinc phosphate lower layer epithelium, the processing of upper layer epithelium) and epithelium handle >
(a) degreasing: commercially available degreasing agent (Fine Cleaner (registered trademark) 6400, Nihon Parkerizing Co., Ltd. system) concentration 20g/L, temperature 60 C, dipping 10 minutes
(b) it washes: tap water, room temperature, dipping 30 seconds
(c) pickling: hydrochloric acid, concentration 17.5%, room temperature, dipping 10 minutes
(d) it washes: tap water, room temperature, dipping 30 seconds
(e) lower layer's epithelium is handled: commercially available trbasic zinc phosphate chemical conversion treatment agent (パ Le ボ Application De (registered trademark) 3696X, Nihon Parkerizing Co., Ltd. system) concentration 75g/L, 80 DEG C of temperature, dipping 10 minutes
(f) it washes: tap water, room temperature, dipping 30 seconds
(g) upper layer epithelium is handled: upper layer epithelium inorganic agent, temperature 60 C, the dipping manufactured in (2-1) 1 minute
(h) dry: 100 DEG C, 10 minutes
The pre-treatment of < comparative example 36 (phosphate/soap processing) and epithelium handle >
(a) degreasing: commercially available degreasing agent (Fine Cleaner (registered trademark) 6400, Nihon Parkerizing Co., Ltd. system) concentration 20g/L, temperature 60 C, dipping 10 minutes
(b) it washes: tap water, room temperature, dipping 30 seconds
(c) pickling: hydrochloric acid, concentration 17.5%, room temperature, dipping 10 minutes
(d) it washes: tap water, room temperature, dipping 30 seconds
(e) chemical conversion treatment: commercially available trbasic zinc phosphate chemical conversion treatment agent (パ Le ボ Application De (registered trademark) 3696X, Nihon Parkerizing Co., Ltd. system) concentration 75g/L, 80 DEG C of temperature, 7 points of dipping
(f) it washes: tap water, room temperature, dipping 30 seconds
(g) soap is handled: commercially available reaction soap lubricant (パ ル ー Block (registered trademark) 235, Nihon Parkerizing Co., Ltd. system) concentration 70g/L, 85 DEG C of temperature, dipping 3 minutes
(h) dry: 100 DEG C, 10 minutes
(i) dry epithelium amount: 10g/m2
(2-4) evaluation test
(2-4-1) processability (pin) test
The test that extrusion process is carried out as the predetermined front end to steel wire, carries out pin test.Pin test is based on Japan The record that Japanese Laid-Open Patent Publication 5-7969 carries out.Lubricity is evaluated with forming load by the height of pin after test.Pin Height is higher, furthermore the more low then lubricity of forming load is more excellent.It should be noted that carrying out pin test based on above-mentioned document When, area amplification degree is set as about 10 times.Load and height of pin when by measurement processing evaluate the lubricity of epithelium.
Evaluation test film: S45C spheroidizing material
Evaluation criteria
◎: significantly excellent compared with phosphate/soap bark film
Zero: excellent compared with phosphate/soap bark film
△: phosphate/soap bark film is same
▲: it is poor compared with phosphate/soap bark film
×: the significance difference compared with phosphate/soap bark film
(2-4-2) processability (draftability is thinned in upsetting-steel ball) test
As the test that the head for being scheduled for bolt is formed, upsetting-steel ball is carried out to steel wire, tension test is thinned.Upsetting Forging-steel ball is thinned tension test and is carried out based on Japanese Unexamined Patent Publication 2013-215773 record.Upsetting-steel ball, which is thinned, stretches examination The area amplification degree tested is up to 150 times or more, and compared with the test of above-mentioned pin, area amplification degree is very big.It therefore, is energy It is enough to reproduce the test for for example forming the processing of the requirement high working property on head of flanged hex bolts.Subtracted by evaluating to enter The ablation amount in thin stretch process face, to can be carried out evaluation to the ablation resistance of epithelium.
Evaluation test film: S10C spheroidizing material
Bearing ball:SUJ2
Evaluation criteria
Have rated has how much area that ablation has occurred relative to thinned Extrude Face entire area.
◎: significantly excellent compared with phosphate/soap bark film
Zero: excellent compared with phosphate/soap bark film
△: same with phosphate/soap bark film
▲: it is poor compared with phosphate/soap bark film
×: the significance difference compared with phosphate/soap bark film
(2-4-3) corrosion resistance (long-term rust prevention) evaluation
To carry out above-mentioned upper layer epithelium and lower layer's epithelium formed the test specimen of processing summer in open environment in doors Situation of getting rusty is observed in exposure 2 weeks or 4 months.The rust area the big, is judged as that corrosion resistance is poorer.
Test specimen: SPCC-SD 75mm × 35mm × 0.8mm
Evaluation criteria
◎: significantly excellent compared with phosphate/soap bark film (rust area is lower than 5%)
Zero: excellent compared with phosphate/soap bark film (5% or more area of rust is lower than 15%)
△: same (15% or more area of rust is lower than 25%) with phosphate/soap bark film
▲: poor compared with phosphate/soap bark film (25% or more area of rust is lower than 35%)
×: significance difference (35% or more the area of rust) compared with phosphate/soap bark film
Test result is shown in table 4.As shown in Table 4, (pin test, steel ball are thinned stretches examination to the processability of embodiment Test), corrosion resistance (especially long-term rust prevention) it is good.Comparative example 19 is the epithelium of only zirconium epithelium, and as a result processability, corrosion resistance be very Difference.Comparative example 20,21 is the example by the film thickness setting of zirconium epithelium out of the range of the present invention.Comparative example 20 is lower layer's epithelium The excessively thin situation of film thickness, as a result corrosion resistance is poor.Comparative example 21 is the blocked up situation of the film thickness of lower layer's epithelium, as a result poor in processability. Comparative example 22~29 be by the quality ratio of silicon and tungsten setting example out of the range of the present invention, have steel ball be thinned draftability and The tendency of corrosion proof result difference.Comparative example 30~33 be containing water-soluble silicate, water-soluble tungstates other than at being allocated as For the example of water-soluble inorganic salt, have the tendency that draftability is thinned in steel ball and corrosion proof result is poor.Comparative example 34 is coating silicon Example of the epithelium of hydrochlorate as lower layer's epithelium fails to obtain corrosion resistance high as the embodiment.Comparative example 35 is to form phosphorus Example of the epithelium of hydrochlorate as lower layer's epithelium.Processability, corrosion resistance and embodiment are peer-level, but since the epithelium contains Phosphorus, therefore there are the phosphatizings such as bolt as described above, therefore not preferably.Comparative example 36 carries out phosphate coating The example of reaction soap processing corrosion resistance compared with embodiment is also poor.In addition, also equally existing the phosphatizings such as bolt with comparative example 35 Problem, phosphate coating are undesirable.About phosphatizing, as shown in comparative example 27,30, containing phosphate as water soluble salt When equally exist.
[table 4]
A possibility that ※ 1 zero: be not situated between phosphorus, and there is no the brittle breaks of the steel wire rod as caused by phosphorus
×: containing phosphorus, there is a possibility that brittle break of the steel wire rod as caused by phosphorus
It can be seen from the above explanation using the steel with the lubricating film containing upper layer epithelium and lower layer's epithelium of the invention When wire rod, the sufficient corrosion resistance in high working property and real-world environment can be taken into account.Therefore, the exploitation value of the present invention industrially Value is very big.
The present invention includes scheme below.
Scheme 1:
A kind of steel wire rod, which is characterized in that it is the steel wire rod with not phosphorous epithelium,
Above-mentioned epithelium successively includes from steel wire rod side: being made of the oxide of zirconium and/or hydroxide and film thickness is 1.0 Lower layer's epithelium of~200nm and containing silicon and tungsten and tungsten/silicon mass ratio 1.3~18 range upper layer epithelium.
Scheme 2:
Steel wire rod according to scheme 1, wherein above-mentioned silicon comes from water-soluble silicate, and above-mentioned tungsten is from water solubility Tungstates.
Scheme 3:
The steel wire rod according to scheme 1 or 2, wherein above-mentioned silicon is from lithium metasilicate, sodium metasilicate and potassium silicate At least one or more, and above-mentioned tungsten is from least one or more in tungstate lithium, sodium tungstate, potassium tungstate and ammonium tungstate.
Scheme 4:
The steel wire rod according to any one of scheme 1~3, wherein contain resin, resin/(silicon in above-mentioned upper layer epithelium + tungsten) mass ratio be 0.01~3.2.
Scheme 5:
Steel wire rod according to scheme 4, wherein above-mentioned resin is selected from vinyl group resin, acrylic resin, ring At least one or more in oxygen resin, polyurethane resin, phenolic resin, cellulose derivative, poly and polyester resin.
Scheme 6:
The steel wire rod according to any one of scheme 1~5, wherein contain lubricant in above-mentioned upper layer epithelium, lubricate Agent/(silicon+tungsten) mass ratio is 0.01~3.2.
Scheme 7:
Steel wire rod according to scheme 6, wherein above-mentioned lubricant is selected from wax, polytetrafluoroethylene (PTFE), fatty acid soaps, rouge At least one or more in fat acid metallic soap, fatty acid amide, molybdenum disulfide, tungsten disulfide, graphite and melamine cyanurate.
Scheme 8:
The steel wire rod according to any one of scheme 1~7, wherein the epithelium of the per unit area of above-mentioned upper layer epithelium Quality is 1.0~20g/m2。
Scheme 9:
A kind of manufacturing method of steel wire rod, which is characterized in that it is the system of steel wire rod described in any one of scheme 1~8 Method is made, range of the steel wire rod surface contact pH 2.5~5.0 and the water system chemical conversion treatment dissolved with water-soluble zirconium compound are made Liquid and form lower layer's epithelium.
Based on Japanese patent application laid of the application by the applying date on March 28th, 2014 is willing to No. 2014-070445 Apply for CLAIM OF PRIORITY, therefore, Japanese Patent Application the 2014-070445th as reference by being introduced into this specification.

Claims (9)

1. a kind of steel wire rod, which is characterized in that it is the steel wire rod with not phosphorous epithelium,
The epithelium successively includes from steel wire rod side: be made of the oxide of zirconium and/or hydroxide and film thickness be 1.0~ Lower layer's epithelium of 200nm and containing silicon and tungsten and tungsten/silicon mass ratio 1.3~18 range upper layer epithelium.
2. steel wire rod according to claim 1, wherein the silicon comes from water-soluble silicate, and the tungsten is from water-soluble Property tungstates.
3. steel wire rod according to claim 1 or 2, wherein the silicon comes from lithium metasilicate, sodium metasilicate and potassium silicate 1 kind or more, and the tungsten one or more of comes from selected from tungstate lithium, sodium tungstate, potassium tungstate and ammonium tungstate.
4. steel wire rod according to claim 1 or 2, wherein contain resin, resin/(silicon+tungsten) in the upper layer epithelium Mass ratio is 0.01~3.2.
5. steel wire rod according to claim 4, wherein the resin be selected from vinyl group resin, acrylic resin, One or more of epoxy resin, polyurethane resin, phenolic resin, cellulose derivative, poly and polyester resin.
6. steel wire rod according to claim 1 or 2, wherein contain lubricant in the upper layer epithelium, lubricant/(silicon+ Tungsten) mass ratio be 0.01~3.2.
7. steel wire rod according to claim 6, wherein the lubricant be selected from wax, polytetrafluoroethylene (PTFE), fatty acid soaps, One or more of fatty acid metal soap, fatty acid amide, molybdenum disulfide, tungsten disulfide, graphite and melamine cyanurate.
8. steel wire rod according to claim 1 or 2, wherein the epithelium quality of the per unit area of the upper layer epithelium is 1.0~20g/m2。
9. a kind of manufacturing method of steel wire rod, which is characterized in that it is the manufacturing method of steel wire rod of any of claims 1 or 2, Make range of the steel wire rod surface contact pH 2.5~5.0 and water system chemical synthesis treatment liquid and shape dissolved with water-soluble zirconium compound At lower layer's epithelium.
CN201580015991.3A 2014-03-28 2015-02-26 The steel wire rod and its manufacturing method of epithelium with excellent corrosion resistance and processability Expired - Fee Related CN106133196B (en)

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JP2014070445A JP6362379B2 (en) 2014-03-28 2014-03-28 Steel wire having a film excellent in corrosion resistance and workability and method for producing the same
JP2014-070445 2014-03-28
PCT/JP2015/055679 WO2015146466A1 (en) 2014-03-28 2015-02-26 Steel wire rod having coating film that has excellent corrosion resistance and workability and method for producing same

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